evaluation of a portable field operated gc/ms instrument

Evaluation of a

Portable Field

Operated GC/MS

Instrument for Air

Emission Purposes

January 2012

Related to Emissions from

Composting Operations & Other

Solid Waste Activities

Final Report – Evaluation of a Portable GC/MS for Air Emission Sampling Objectives – January 2012

Table of Contents Executive Summary ....................................................................................................................................... 2

Introduction and Scope ................................................................................................................................. 3

Sampling Teams ............................................................................................................................................ 3

Sites ............................................................................................................................................................... 4

Sample Locations .......................................................................................................................................... 4

Sample Collection ......................................................................................................................................... 4

Analysis ......................................................................................................................................................... 8

Results ........................................................................................................................................................... 9

Site A ......................................................................................................................................................... 9

Site B ....................................................................................................................................................... 12

Site C ....................................................................................................................................................... 14

Sample/Site Specific Observations on Data Collected ................................................................................ 15

Conclusions & General Observations .......................................................................................................... 18

Recommendations ...................................................................................................................................... 20

Appendices

Appendix A – Analysis Report, KD Analytical, June 2011

Appendix B – Evaluation Report, California EPA, HAPSITE® Portable GC/MS, March 2004


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Executive Summary

This report contains the findings of a field demonstration of a portable Gas Chromatography/Mass

Spectrometry (GC/MS) unit for air analysis. The main purpose of the sample collection and analysis was

to demonstrate the technology for VOC speciation for air surveys. Three sites were sampled for one day

each on June 21-23, 2011. The sites were identified as Site A, B, and C. Site A was a totally enclosed yard

waste composting facility, Site B was an outdoor aerated static pile compost facility processing yard

waste and food waste, and Site C was a 51 year old, active landfill (with capped areas). Air downwind of

wastewater aeration processes at Sites B and C was also tested. Both point source and ambient air

samples were collected.

The GC/MS unit was found to be viable as a portable unit that can be hand carried, using its own battery

pack, transported by a vehicle while powered by a car battery, or stationary and powered by 120 Volt

AC. Sample collection and analysis took less than 30 minutes per sample. Results were available real-

time on-site. Using the knowledge of sample results the team could make informed choices on where to

collect further samples or where to move on and focus on other areas. Two ranges were available for

analysis – a higher ‘parts-per-million (ppm)’ range and a lower ‘parts-per- billion (ppb)’ range. The unit

can speciate over 750 compounds using both an on-site calibration standard and accessing an internal

computer library for peak identification.

The GC/MS unit has potential to provide both screening levels of emission evaluations and more

rigorous emission factor or emission rate types of evaluations. It was a cost effective and efficient

approach to collecting a lot of air emission characteristic data. Its effective use in guiding air emission

testing could save time, save money, and improve the focus to the air emission characterization work. It

also could possibly provide more confidence by others in that effort by supporting the knowledge that

all of the important emission points and most of the important compounds of interest have been

identified in the study.


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Introduction and Scope This work was conducted under an interagency agreement (NO. C1100195) and partnership between

the State of Washington Department of Ecology (Ecology) and Puget Sound Clean Air Agency (PSCAA) for

the purpose to increase understanding of emissions from solid waste facilities through the use of a

mobile GC-MS. A contractor was hired to take a ‘snap shot’ of emission profiles from three solid waste

handling facilities in western Washington.

Goals were to

1. Evaluate the mobile GC-MS technology to provide speciated field emission results with a trained

instrument operator

2. Use the mobile GC-MS technology to evaluate solid waste facility emission profiles

3. Increase the state’s understanding of emission profiles from different processing and storage

areas within compost facilities

Objectives were to

1. Coordinate with other agencies to sample emissions from at least one compost facility using

standard sampling methods and the mobile GC-MS for all samples. PSCAA was NOT responsible

for emissions sampling using standard methods.

2. Compare results from mobile GC-MS technology to standard emission sampling results.

3. Report on the value and reliability of mobile GC-MS technology for evaluating compost facility

emissions.

KD Analytical was hired as a subcontractor. They provided the portable GC-MS manufactured by Inficon

and an instrument operator who performed sampling, analysis, and data interpretation.

This report contains details of the sampling events, analytical results, and recommendations for the

value and reliability of this technology.

Sampling Teams Shaun Vibert, Director of Training, KD Analytical, was the GC/MS analyst for this effort. Additional off-

site support was offered by KD Analytical employees Craig Crume, Vice President, and Dan Schenk, West

Coast Regional Manager. PSCAA employees, Claude Williams, Engineer, and Melissa McAfee, Inspector,

were on site to help with sample planning and to collect bag samples on all days. On each day a PSCAA

supervisor was on site as follows: Steve Van Slyke (Day 1), Mario Pedroza (Day 2), and Rick Hess (Day 3).

Adam Petrusky, PSCAA Air Monitoring Specialist, joined the team to evaluate the GC/MS technology on

Day 2.

For each day a site manager was present as an escort. The site manager educated the team on the

process, gave safe access around moving trucks and loaders, and helped with any needs like access to

sample ports, freshly transferred materials and power.


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Sites Three sites were surveyed with the GC/MS:

1. Site A: An indoor compost facility with outdoor curing/finish piles and bio-filters. This site

accepts only yard waste and land clearing debris.

2. Site B: An outdoor aerated static pile compost facility that uses positive aeration, or negative

aeration with bio-filter controls. This site accepts yard and food waste. It also accepts paunch

waste from a meat packing plant. Paunch wastes are the stomach contents of cattle after

processing.

3. Site C: A 51 year-old active capped municipal landfill that accepts nearly one-million tons of

waste per year.

Sample Locations Each day the sample team met on site and determined sample locations. The team made a plan to

characterize each site from initial receipt of materials to finish piles. Air samples for bio-filters at the

compost facilities were collected both at the inlet plenums and over the bio-filter surfaces for exhausts.

Air samples near wastewater aeration treatment were also tested at sites B and C.

Because site C is mostly filled and capped, the team drove around the perimeter of the site and

collected samples along the fence-line with the only process points being the active tipping face and

wastewater lagoons. This site is representative of an ambient air sampling demonstration for this

technology. All samples except the active tipping face, where a bag sample was collected, were taken

directly with the GC/MS. The use of the unit in this application showed that it was indeed portable and

capable of collecting samples to characterize fence-line levels at a large acreage site in a timely (half a

day) manner.

Sample locations are described below with the tables of sampling results for each site.

Sample Collection Site A was sampled on Day 1, Jun 21; Site B was sampled on Day 2, Jun 22; and Site C was sampled on

Day 3, Jun 23, 2011. In general, sampling was conducted from the back end of the process first and then

moving forward. This was planned to ensure that the GC/MS column was not ‘blown out’ by the highest

concentration samples (expected to be at the beginning of the process, for example in a compost tipping

building) at the start of the day. That is, if too high of a concentration of a sample goes through the

instrument, then valuable time must be spent to flush and clean the instrument to get it back to a

normal baseline before sampling can be resumed. This is the same for analyses conducted in a

laboratory. While this precaution was taken, it never became a problem on any of the 3 days.


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Figure 1: Real Time Sample Collection & Measurement using Portable GC/MS

Samples were collected in three ways:

1. By holding the GC/MS probe over a pile (within 12”) or in the ambient air and sending the

sample directly to the instrument.

2. By using a Tedlar sample bag and allowing positive pressure air from the ductwork to fill the

bag.

3. By using a Tedlar sample bag and filling it with air from over a pile (within 12”), from ductwork

or from below a grate. An SKC Vacu-chamberTM was used to fill the bag using a pump.

Figure 2: Tedlar Bag Sampling with Pump, Vacu-ChamberT M , & Teflon Tube


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Bags were pre-purged with sample per the sampling procedure. New bags were used for each sample.

The GC/MS portable unit weighs about 40 pounds, so it was helpful to drive around each site. Samples

were collected directly over piles or from ambient air. The unit takes 10-30 minutes to sample, analyze,

and re-calibrate. Data analysis and interpretation can take an additional 30 minutes per sample.

The GC/MS unit requires power. For this effort a special inverter was used to connect it to the car

battery for power. The analyst also brought 2 batteries for the unit each with a 2-3 hour life. It also ran

with an extension cord to 120 Volt power.

Figure 3: GC/MS Unit in the Back of a Car with Power to the Car Battery

The Tedlar bags offered the advantage of being able to collect a large number of samples in a short

amount of time (as many as 10 bags in an hour). The GC/MS analyst could then conduct analyses on or

off-site and after hours as needed. For example 3 sites were fully characterized in this project. Because

over half of the samples were collected in bags while the GC/MS unit was simultaneously collecting and

analyzing samples on site, sampling at each site was completed within a day (and once within 4 hours).

The bags also allow the analyst to make dilutions as needed for the dirtier or higher concentration

samples. As mentioned above this protects the instrument because a higher concentration sample can

dirty the GC/MS components and make it go off-scale where it would take longer to flush and clean

before resuming a zero baseline.


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Figure 4: Logging Sample Bags after Collection

The bags also allow the analyst to make dilutions as needed for the dirtier or higher concentration

samples. As mentioned above this protects the instrument because a higher concentration sample can

dirty the GC/MS components and make it go off-scale where it would take longer to flush and clean

before resuming a zero baseline.

For future work, the collection of a sample into a bag or other container (like a Summa canister) allows

for time integrated sampling. While the GC/MS collects a sample instantaneously in 1-2 minutes, a time

integrated sample with a flow controller into a bag or other container can take a sample over a desired

period of time like an hour or day.

The analyst reported some interference (possibly phenolic) from the new Tedlar bags. The report states,

“Some samples compounds were identified, but unable to be semi-quantified due to tedlar bag

contaminant interference.” This flag was attached to 3 of the Day 1 samples. They suggested the use of

more expensive Teflon bags as a remedy in the future. Also the smallest bags (<1 liter) can be used as

very little sample volume is needed for analysis. Teflon tubing was used as a sample probe when

needed for collecting bag samples over a pile.

Bag samples collected from ductwork were quantitative. Flow rates were not collected to determine

emission rates. However, the concentrations measured and reported would be quantitatively

representative of the process. It is important to note that when a probe was held over a pile for direct

GC/MS measurement or sample bag collection, the value would be qualitative or semi-quantitative. The


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amount of dilution from ambient air would not be known, and while compounds could be identified and

some relative concentration strengths of their presence could be measured, these values would not be

quantitative emission rates. More elaborate sampling protocols like flux chamber sampling would be

needed to collect quantitative samples, which was beyond the scope of this work. Ambient samples

would be quantitative, and Site C is a good representation for that application.

Analysis The GC/MS took real-time samples and gave on-site results. Appendix A provides the complete Analysis

Report provided by KD Analytical following the field work. There are 2 ranges, high (ppm) and low (ppb),

which can be used for the instrument. For example the first sample collected over a bio-filter area at

Site A was analyzed on the high range. Results were not detectable. The sample was then re-collected

and re-analyzed on the lower range. Results in parts per billion (ppb) levels were found. Sample results

for this sample are shown below as Sample A-1a and A-1b, respectively.

Looking at Sample A-1b results, as an example, shows the following analytical information:

1. Each compound has a distinctive retention time on the chromatogram with ethylfuran coming

out (eluting from the column) first at 3 minutes 24 seconds and a pinene-like compound coming

out last at 12 minutes 19 seconds.

2. Looking at ethylfuran the area count was 1744914. The area count for the 20 ppb standard was

22974792. The approximate compound concentration was then derived as a 1:1 ratio of the

unknown to the known: 1744914/22974792 = Sample Result/20 ppb, and the sample result was

1.5 ppb.

3. Five compounds were detected: ethylfuran, toluene, pinene, 3-carene, and limonene with

multiple pinene and pinene-like compounds reported. Values ranged from 1.5 ppb for

ethylfuran to 15.4 ppb for limonene. Toluene and pinene-like compounds were identified but

not quantified.


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Results

Site A The sample log for Site A is shown below. Samples A-2 through A-8 were associated with air drawn from

the building and from positive and negative aeration compost piles inside the building. These samples

were collected in reverse order of the process, so A-2 represents the plenum pulling from the end of

Phase II and A-8 represents the plenum pulling from the beginning of Phase I.

Sample A-13 was pulled over fresh wood chips. These are typical wood chips that could be used to build

or refurbish a biofilter. This sample is representative of emissions over a new bio-filter with no process


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exhaust. Over time the wood chips would age (turning from orange brown to gray just as garden bark

would), and the odors and emissions could change.

A-1a GC/MS probe over south biofilter outside – draws from building interior (ppm range)

A-1b GC/MS probe over south biofilter outside – draws from building interior (ppb range)

A-2 Bag sample from indoor positive flowing duct end of phase 2 bio-filter inlet at Fan #15

A-3 Bag sample from indoor positive flowing duct biofilter inlet at Fan #14





A-8 Bag sample from indoor positive flowing duct biofilter inlet near start of Phase I

A-9 Bag sample from probe over freshly dumped curing pile outside (loader moved from Phase II

inside building to outside in covered area next to the building within the hour), steam emissions

observed from pile

A-10 Bag sample from probe over aged curing pile outside in covered area

A-11 Bag sample from probe over screened finish product (screen not running) outside in covered

area

A-12 GC/MS probe over older biofilter outside

A-13 GC/MS probe over fresh wood chips outside – representative of emissions from new chips

comprising a biofilter


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Page 12 of 20

Site B The sample log for Site B is shown below. All samples were outside of buildings except for those

collected in the Tipping Building.

B-1 GC/MS probe over Saturday screened finish product pile (sampled on Wed)

B-2 GC/MS probe over final curing pile – freshly dumped by loader bucket

B-3 GC/MS probe over Phase 1 to Phase II freshly moved pile

B-4 GC/MS probe over South Bio-filter (draws from Phase I negative aeration)

B-5 GC/MS probe over North Bio-filter (draws from Phase I negative aeration)

B-6 Bag sample in tipping building – freshly dumped green waste, grass and existing paunch

B-7 Bag sample from duct newest Phase I pile – negative draw of air through duct to bio-filter inlet

B-8 Bag sample from duct oldest Phase I pile – negative draw of air through duct to bio-filter inlet

B-9 Bag sample from duct middle-age Phase I pile – negative draw of air through duct to bio-filter

inlet

B-10 Bag sample from under sidewalk grate over leachate collection well after weir drop and before

aeration pond

B-11 Bag sample with probe held over freshly dumped material in Tipping Building – food and green

waste

Figure 5: Bag sampling - Fresh Food and Green Waste in Tipping Building


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Table 2: Site B Day 2 Sample Results (ppb) for Samples B-3 through B-9 (+)

Compound B-3

B-4

B-5

B-6

B-7

B-8

B-9

Acetone 24.9

Butene Detect Detect

Ethanol 91.3

Dimethyl sulfide 1.9 3.5 5100 368.6

2-Butanone 1.9 Detect 2.2 6.2 1500 30.9 61.5

2-Butanol 28.3 113.4

Methyl-Cyclohexane

10.8

Methyl furan Detect

Ethyl furan Detect Detect

Heptane Detect 23.5 69.7

Toluene 3.0 2900 16.9

Pentanoic Acid 31.0

Butanoic Acid 51.6 15.8

Butanoic acid, ethyl ester

15.4

Octane 11.6 1800 17.1 101.0

Nonane 1300 45.8

Pinene-like compounds

Detect Detect Detect Detect Detect Detect Detect

Pinene 11.6 7.7 27.4 169.2 124800 842.9 6409.8

3-Carene 2.8 1.9 83.9 70.7 11800 431.3 1583.6

Limonene 28.1 18.6 77.5 230.6 21700 818.0 228.8

^Cyclohexadiene Detect Detect

methyl (methylethyl) cyclohexene

Detect

Methyl-(methylethyl)-

benzene Detect Detect

Notes: Compounds listed as (Pinene*) are Pinene-like compounds that cannot be definitively identified without component and instrument specific research. Pinene concentration is greater than reported. Full area could not be attained due to a concentration above method detection limits. ^Cyclohexadiene compound type cannot be specified (+)Samples B-1 and B-2 were not detected <1 ppb. Sample B-10 had 2100 ppb limonene and toluene was

detected but not quantified. Sample B-11 had 1100 ppb limonene as the only compound detected and

measured.


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Site C All of the samples collected at Site C were ambient air samples. All were collected directly with the

GC/MS probe except for C-2 which was collected into a sample bag with the vacu-chamberTM and pump.

The sample log for Site C is shown below:

l

C-1 Perimeter Road north of the water tower by main hill

C-2 Active face with truck dumping, open garbage, and loader operations

C-3 Pipe farm just inside Perimeter Road south of flare station. Wind from South 1-4 mph

C-4 Perimeter Road west side, area 4, next to well 4W020101

C-5 South of contaminated storm water pond

C-6 Leachate Extraction pump station

C-7 Perimeter Road south of pump station

C-8 Perimeter Road by water sampling well W-76

Only one sample, C-2, collected from the vicinity of the active face with trucks tipping garbage and

loaders moving garbage, had detectable compounds for this site. These sample results are shown below

in Table 3. All other sample results were not detectable at parts-per-billion levels, <1 ppb.


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Figure 6: Bag Sample C-2 Collected Downwind in Vicinity of Active Face at Landfill

Of notable interest was that while sampling at a few locations like downwind of the aerated wastewater

pond, the team experienced a low level odor, however the instrument showed nothing detectable. This

is a reminder that the nose can detect odors that instrumentation may or may not detect. Also some

odors have a VOC component, and others do not.

Sample/Site Specific Observations on Data Collected

1. The most common compounds identified and in the highest concentrations for the compost facilities

(Sites A and B) were the terpenes: pinene, 3-carene, and limonene. Per Wikipedia the terpenes are

defined with these characteristics:

Pinene is a constituent of pine resin also found in the resins of other conifers and non-

coniferous plants. Pinene is insoluble in water.

Table 3: Site C Day 3 Sample Results for C-2 (ppm)

Compound Concentration

Hexane 1400

Methylcyclopentane

Heptane

Methylcyclohexane

Toluene 2000

Dimethylcyclohexane

Ethylhexane

1-chloro-4-(trifluoromethyl)-Benzene

2600

Ethylbenzene 1800

m, p-xylene 4900

o-xylene 1100

Nonane

Methylethylbenzene

Trimethylbenzene

Decane

Limonene 1900


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Limonene is a liquid hydrocarbon with the smell of oranges. It is also prevalent in the rind of a

lemon, where it gets its name.

Carene occurs naturally as a constituent of turpentine. It has a sweet pungent odor, and is

insoluble in water.

2. Site C (a landfill) had limonene (1900 ppb) and no pinene or 3-carene detected in the ambient air

sample at the active face, C-2. Other compounds identified in this sample were m,p-xylene (4900

ppb), 1-chloro-4-(trifluoromethyl)-benzene (2600 ppb), toluene (2000 ppb), ethylbenzene (1800

ppb), hexane (1400 ppb), and o-xylene (1100 ppb).

3. As expected, the highest sample for Site A was A-8 from ducting to the biofilter inlet representing

the newest start of Phase I with these results: 39,000 ppb pinene, 26,800 ppb 3-carene, and 21,500

ppb limonene. Similarly the highest sample results for Site B were from Sample B-7, the sample

from ducting to the bio-filter inlet representing the newest Phase I pile: 124,800 ppb pinene, 11,800

ppb 3-carene, and 21,700 ppb limonene.

4. Other compounds identified in sample B-7 were dimethyl sulfide (5100 ppb), toluene (2900 ppb),

octane (1800 ppb), 2-butanone (1500 ppb), and nonane (1300 ppb). The toluene (2900 ppb) was a

compound in common with C-2 from the active face ambient air where toluene was 2000 ppb.

Sample B-10 from the headspace over the leachate collection well showed 2100 ppb limonene and

toluene identified but not quantified, and Sample B-11 from freshly dumped yard and food waste in

the tipping building showed 1100 ppb limonene only.

5. The progression of the process, showing mostly decreasing concentrations indicating degradation

and a few increasing concentrations indicating formation across Site B, can be illustrated by looking

at these samples collected from ductwork to the bio-filter inlet from the newest phase I pile (Sample

B-7), to the middle of Phase I (Sample B-9), to the oldest Phase I pile (Sample B-8). These results are

shown in Table 6 below.

Table 6 Progression of Composting Process Phases Related to Changing Emission Profiles

(Site B, All Concentrations Reported in ppb)

Compound B-7 (Start) B-9 (Middle) B-8 (End)

Dimethyl sulfide 5100 368.6 --

2-Butanone 1500 61.5 30.9

2-Butanol -- 113.4 28.3

Heptane Detected 69.7 23.5

Toluene 2900 16.9 --

Pentanoic Acid -- -- 31.0

Butanoic Acid -- 15.8 51.6

Butanoic Acid, ethyl ester

-- -- 15.4

Octane 1800 101.0 17.1

Nonane 1300 45.8 --

Pinene 124800 6409.8 842.9

3-carene 11800 1583.6 431.3

Limonene 21700 228.8 818.0


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6. Note that limonene and toluene were detected over the wastewater leachate collection well, so

these compounds could be carried off (causing decreases in the solids) in the wastewater leachate.

It makes sense that the volatile organic acids like pentanoic acid and butanoic acid and an alcohol

like 2-butanol could be formed with the bacterial activity in the piles.

7. The freshly moved pile from Phase I to Phase 2, Sample B-3, showed lower levels (1.9 to 28.1 ppb)

of pinene, 3-carene, and limonene with the addition of a possible breakdown product, acetone (24.9

ppb). No compounds were detected (<1 ppb) in the air pulled over the final screened material or

cure piles indicating complete degradation or volatilization of these compounds by the time the

material becomes the finish product.

8. The Phase I start to end of Phase 2 process was characterized with almost twice as many samples at

Site A. As would be expected the data shows not much difference between samples collected in

the ductwork from adjacent fans to the bio-filter inlet. These samples are almost representative of

duplicate samples and definitely show reproducible values for many results and on the same orders

of magnitude for other results. For example, 2-butanone is roughly the same for Samples A-5

through A-8 with values of 1100, 1100, 1200, and 1300 ppb.

9. Results for Site A for limonene shows degradation over the process from Sample A-8 (start of Phase

I) to A-3 (end of Phase 2) with values in ppm declining as follows: 21.5 (A-8), 19.4 (A-7), and then

leveling at 13.1 (A-6), 12 (A-5), 10.5 (A-4), 8.9 (A-3), and 11.4 (A-2).

10. Similarly a decline and then reproducibility can be found for pinene and 3-carene for these samples.

For pinene results in ppm start at 39 (Sample A-8), and then decrease to 31 (A-7), 21.1 (A-6), 14.6 (A-

5), before they level off at 12.8 (A-4), 13.3 (A-3), and 11.3 (A-2). For 3-carene results in ppm start at

26.8 (Sample A-8), and then decrease to 11.2 (A-7) and 14.1 (A-6) before leveling off at 4.7 (A-5) and

4.4 (A-4) to 2.2 (A-3). The result for 3-carene for Sample A-2 then goes up to 8.5 ppm.

11. The bio-filter exhaust for Site A shows these same constituents but at a low part per billion level (<

15.4 ppb) for pinene, 3-carene, limonene, and ethylfuran with toluene detected but not quantified.

Ethylfuran was not detected in any other sample for this site.

12. For Site A, volatile organic acids were not identified except for 1800 ppb butanoic acid in Sample A-

3.

13. The sample from over the fresh wood chips (Sample A-13) showed 733 ppb 3-carene and 146 ppb

limonene. Comparing these results with Sample A-8, the start of the Phase I process, shows much

higher levels in the process with pinene at 39,000 ppb, 3-carene at 26,800 ppb, and limonene at

21,500 ppb. Therefore, the pinene, 3-carene, and limonene were most likely incoming with the

feedstock for this site and not from any mixing with wood chips. These values were comparable to

the levels of these compounds for Site B at the start of Phase I where pinene was higher at 124,800

ppb, but limonene was nearly the same at 21,700 ppb and 3-carene was half as much at 11,800 ppb.


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Conclusions & General Observations

1. The portable GC/MS evaluated was a useful as a survey tool for air emissions. It provides VOC

speciation information for over 750 compounds which goes far beyond traditional portable tools

such as an Organic Vapor Analyzer for total hydrocarbons, or a Lower Explosive Limit meter for

flammability, where there is no identification of compounds present.

2. The unit gives real time results which can then be used to identify hotspots for further sampling.

Using the instrument can give guidance on where it is best to collect samples for laboratory

analyses. For example, in this study, when results were ‘not detectable’ for screened finish

materials and finish piles, the team did not collect further samples of finish piles and product. The

team was able to then focus on the front end of the process for further study.

3. The unit provides results for a wide range of compounds that would require several sampling and

analytical methods if currently available and conventional methods were to be used. As an example,

the compounds identified and quantified at Site B included regular TO-15 compounds (e.g. toluene ),

alcohols (e.g. ethanol), reduced sulfur compounds (e.g. dimethyl sulfide), and volatile organic acids

(e.g. butanoic acid). The analysis also provides concentrations for compounds which are not

included in standard “over the counter” air sample analytical services. Asking the laboratory

completing a regular TO-15 canister analysis to identify and quantify all of the resolvable peaks in

addition to the standard compound list for the method adds both cost and time for each analysis.

4. There were occasions, like at the landfill aerated leachate runoff pond, where the team experienced

an odor and got no VOC species detected per the instrument. This is consistent with odor science,

where the nose is known to be one of the most sensitive detectors. Some VOCs are odorous and

others are not; while some undetected compounds like hydrogen sulfide and ammonia are odorous

but are not volatile organic compounds.

5. It is possible to use a device called a “concentrator” to accumulate samples prior to analysis. This

was not used or evaluated in this study. The use of a concentrator could allow for time integrated

sampling and detection of compounds at even lower levels. For example, instead of ambient

sampling results of <1 ppb, a concentrator could yield detectable results at lower levels like parts

per trillion.

6. More samples can be pulled and analyzed on site to minimize uncertainties for heterogeneous

areas, and conversely fewer samples can be taken if results are, for example, well characterized or

not detectable, depending on the sampling objectives. This prevents useless samples being

submitted to the laboratory for costly analysis.

7. The unit continued to operate while driving over bumpy roads and while moving it in and out of the

vehicle and around each site. It did not appear to be sensitive to heavy handling, movement, and

field conditions.

8. The unit worked well in ppb and ppm levels for the composting and landfill sites. Samples were all

within the instrument’s ranges and at no time did it go off-line and spike over normal ranges. It is

similar to laboratory instrument analysis in that the instrument range and sensitivity are affected by

the highest concentration compounds in the samples which are loaded onto the chromatography

column. If those higher concentration compounds force the instrument to operate in the “ppm”


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range, then it will be more difficult to identify and quantify the peaks that are in the lower “ppb”

concentrations. Discussions with KD Analytical staff indicated that customized setup and instrument

operational control can focus on certain compounds and improve that outcome (e.g. quantify a

smaller compound peak when larger concentrations are present). This would clearly need the

trained and knowledgeable operator that is discussed below.

9. Moisture was not a concern during this work to evaluate the technology. No samples were

observed to have moisture.

10. The unit does not run like a “point-and-shoot” camera. It requires a trained operator for

calibrations, operation, and data interpretation. Per a KD Analytical 2009 brochure, “From Classic to

ER: A Brief Report on the Differences between HAPSITE® Iterations”, they noted that ”the instrument

has been relegated to ‘door stop’ status in the First Responder community for anyone who did not

have the time, sustainment money or training to properly use the equipment. Those who did learn,

upkeep, and utilize their instruments correctly found them to be very much primary analysis

instrument on most responses.”. The operator that demonstrated the instrument during this

evaluation clearly had the experience to efficiently operate the device. However, that experience

also extended to the ability to interpret the results the instrument produced through the use of

computer tools linked to the technology and report out information that met QA/QC protocols.

11. A wide range of user survey results summarized in a California EPA evaluation report identified

additional advantages/benefits and disadvantages/limitations for the HAPSITE® technology. A copy

of that report is provided in Appendix B.

12. Additionally data analysis and interpretation takes training and experience. KD Analytical offers

consulting on an annual or hourly basis to support maintenance, parts, plans, training, and data

analysis.

13. It was not possible to align the field work for this technology evaluation with the composting air

emission sampling project managed by Washington State Department of Ecology that was underway

in the same month. The field work for these two projects was different by approximately one week

and the Ecology sampling effort was completed at sites that were not available to this project for

evaluation. So, the interest in having parallel sampling and analysis work using different technical

approaches to allow comparison was not achieved directly during this evaluation project.

14. Even though the parallel effort described above was not completed, KD Analytical provided

reference material that did include a comparison of results (under controlled circumstances) for

HAPSITE® analytical performance relative to US EPA Method TO-15 work. That information is in a

report titled “Evaluation Report for HAPSITE® by Inficon for the California EPA Department of Toxic

Substances Control and California Environmental Technology Certification Progam, March 2004” and

a copy of that report is provided in Appendix B of this report. In that California EPA report (p 28-30),

the California DHS Environmental Health Laboratory did a study in 2002 to compare the HAPSITE®

to laboratory GC/MS analyses for 8 analytes: MTBE, chloroform, 1,1,1- TCE, carbon tetrachloride,

benzene, chlorobenzene, m-xylene, and toluene. They found the HAPSITE® was comparable to

laboratory analyses using US EPA Method TO-15. The HAPSITE® also demonstrated an advantage in

analyzing high concentration samples. The study found good correlation of HAPSITE® data from

samples in Tedlar bags compared to laboratory data from samples in Silicocanisters. Finally the

study demonstrated the stability of samples in Tedlar bags analyzed within 2 hours of collection.


Page 20 of 20

Recommendations

1. The field GC/MS system evaluated is a viable and technically powerful tool for screening levels of air

sampling and analysis work, even for complex emission profiles. As a screening tool, it could

support any or all of the following objectives:

Identify what compounds may be present

Identify levels of compounds present to determine if they may be present in sufficient quantity

to warrant further evaluation

Identify where compounds of interest are being released on a large or diverse site

Evaluate the variability of specific emission units over a focused period of time

Evaluate the variability of specific emission units in response to operationally controlled

variables (e.g. sensitivity of emission changes to variables)

2. The field GC/MS system evaluated is potentially a viable technology for emission rate development

work once an initial evaluation verified the specific compounds objectives are resolvable and

quantifiable out of the mixture of compounds present. This recommendation for use to develop

emission rate or emission factor information is conditional on the basis that sampling method

technical requirements are met and consistent with the field GC/MS instrument operations. The

field GC/MS will only provide concentration information and additional work is necessary to convert

that information into rate based data.

3. Either recommendation identified above should be accomplished by trained and competent

instrument operators. In discussions with the KD Analytical representatives, it is clear that the

instrument use is clearly a teachable skill and others have done it. However, the level of skill

observed during this field evaluation was highly developed and in the end, very important to

completing the amount of quality work in short time that was available. For anyone considering

buying or renting one of these instruments, the level of training and actual operational experience

needed to be good at the open-ended screening study should not be underestimated. Using this

technology with the support of this type of experienced operator was cost effective for this project

and would likely be so with either of the recommendations identified above.

APPENDIX A

Analysis Report

Puget Sound Clean Air Agency Seattle, WA

June, 2011

Puget Sound Clean Air Agency On-site Analysis Report

June, 2011

Background:

The Puget Sound Clean Air Agency contracted KD Analytical to demonstrate field use of

a mobile and field-portable gas chromatograph – mass spectrometer (GC/MS) to take a

‘snap shot’ of emission profiles from various compost/landfill facilities in western

Washington. The HAPSITE® GC/MS manufactured by INFICON can identify and

provide semi-quantitative concentration results for a broad range of volatile organic

compounds.

Shaun Vibert of KD Analytical conducted the sampling and analysis for these events.

Chemical Concentrations:

Chemical concentrations were determined by comparing the identified compound to

the known concentration of the internal standard Bromopentafluorobenzene (BPFB).

The semi-quantitative chemical measurements in this report for the sample results are

presented in parts per billion by volume (ppbv), and parts per million by volume (ppmv).

Sample Location

The locations for sampling during these events were determined by Puget Sound Clean

Air Agency personnel.

Analytical System (INFICON HAPITE® GC/MS)

The INFICON HAPSITE® portable GC/MS was designed specifically for the analysis of

volatile compounds. The HAPSITE® is a full featured quadrupole GC/MS.

The HAPSITE® GC/MS uses a sampling wand with an internal pump to collect the

sample. The sample is pulled into a concentrator tube with variable injection capabilities.

The column is a 30 meter DB-1 with a 3 meter backflush column. The backflush column

allows the volatile organic target compounds to get onto the column, then backflushes off

the non-target semi-volatile compounds. The interface between the GC and MS is a

methyl silicone membrane. This membrane allows organics to migrate through to the MS

while sweeping most non-organics out through the vent.

By minimizing what gets into the MS, this instrument is able to utilize a chemical ‘getter’

pump rather than a mechanical pump. The getter pump maintains adequate vacuum for

months at a time.


June, 2011

The analyses time on the HAPSITE® GC/MS is typically 15 minutes. The HAPSITE

®

GC/MS co-injects two compounds as internal standards with every analysis. These

compounds are used for additional QA/QC for each analysis. The compounds are

Bromopentafluorobenzene, and 1,3,5 Tris (trifluoromethyl) benzene.

Table 1: Operating Conditions

Instrument Serial # D7HS10A00008P

Column Temperature (C) 60-160

Membrane Temperature (C) 70

Valve Oven Temperature (C) 70

Probe Temperature (C) 60

NEG Temperature (C) 480

Concentrator Elbow Temperature (C) 70

Heated Line Temperature (C) 70

Analysis Time (minutes) 15.0

Quality Assurance/Quality Control:

The following steps were taken to ensure that the data collected during the analytical

events were of usable quality:

Mass Spectral Ion Intensity Verification

The mass spectral ion intensities were verified at the beginning each day of analyses.

They were verified using the manufacturer’s mass calibration criteria. Tune verification

is considered valid for 12 hours, at which time the instrument will auto-tune again.

Blanks

Blank samples were analyzed prior to sample collection to ensure that there was no

carryover affecting results.


June, 2011

Some samples compounds were identified, but unable to be semi-quantified due to tedlar

bag contaminant interference.

Compounds listed as (Pinene*) are Pinene-like compounds that cannot be definitively

identified without component and instrument specific research.

Quantification was provided only for a component which qualified through the specific

methods’ detection criteria. Therefore compounds detected at less than 1ppmv or less

than 1ppbv for a given method where not quantified.

Spectral match values utilizing NIST reference data where required to be at a minimum

of 700 (70%) in order to facilitate a final call value.

Compound IdentificationRetention

TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

None N/A N/A N/A N/A N/A N/A

Sample ID: A-1a

Sample Date: 21JUN11

Sample Time:Notes: No compounds detected within instrument parameters

(ppm level detection range)

DataFile Name: Air_Tri-Bed_PPM_Standard_20110621_002

Sample Location:

PSCAA GC-MS Evaluation Data - Site A Final.xlsx Prepared by KD Analytical A-1a


TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

Ethylfuran 3:24 762 1744914 22974792 20 1.5

Toluene 4:54 836 959083

Pinene* 9:55 3654622

Pinene 10:04 930 14831494 22974792 20 12.9

Pinene* 10:18 2836401

Pinene* 10:38 47364588

3-Carene 11:12 891 12617642 22974792 20 11.0

Limonene 11:26 885 17743810 22974792 20 15.4

Pinene* 12:10 3563287

Pinene* 12:19 1883713

Sample ID: A-1b

DataFile Name: Air_Tri-Bed_PPB_Standard_20110621_001

Sample Location: Sample Date: 21JUN11

Notes: Compounds listed as (Pinene*) are Pinene-like compounds

that cannot be definitively identified without component and

instrument specific research.

Sample Time:

PSCAA GC-MS Evaluation Data - Site A Final.xlsx Prepared by KD Analytical A-1b


TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

(ppm)

Acetone 1:41 927 4811072 17237552 5.37 1.5

2-Butanone 2:10 902 2632756

2-Pentanone 2:41 729 1358784

Hexanoic acid, methyl ester 9:34 864 1586984

Pinene* 9:54 919313

Pinene 10:04 916 36189240 17237552 5.37 11.3

Pinene* 10:39 17486486

Pinene* 10:45 36952716

3-Carene 11:13 922 27412272 17237552 5.37 8.5

Limonene 11:25 925 36610760 17237552 5.37 11.4

Pinene* 12:10 3923616

Pinene* 12:20 10762722

Pinene* 12:27 14096566

Pinene* 12:49 2465585

Pinene* 13:15 9566624

Sample ID: A-2





Sample Time:


Sample Location:

PSCAA GC-MS Evaluation Data - Site A Final.xlsx Prepared by KD Analytical A-2


TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

(ppm)

Acetone 1:39 900 7355727 14700976 5.37 2.7

2-Butanone 2:10 935 2684611

2-Pentanone 2:39 750 1445004

Butanoic acid, methyl ester 3:42 787 553153

Butanoic Acid 5:41 812 5046752 14700976 5.37 1.8


Pinene* 9:54 1019084

Pinene 10:04 918 36386880 14700976 5.37 13.3

Pinene* 10:39 40364620

Pinene* 10:45 45305184

3-Carene 11:12 898 6013157 14700976 5.37 2.2

Limonene 11:26 900 24488972 14700976 5.37 8.9

Pinene* 12:10 3937718

Pinene* 12:20 12908275

Pinene* 12:27 14587179

Pinene* 12:48 2931196

Pinene* 13:14 11801084

Sample ID: A-3






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

(ppm)

Acetone 1:40 945 819988

2-Butanone 2:09 896 3343540

2-Pentanone 2:40 750 2126833

Methylbutanal 2:47 2029213



Pinene* 9:55 1379450

Pinene 10:05 927 50517924 21147558 5.37 12.8

Pinene* 10:39 30845184

Pinene* 10:45 50629432

3-Carene 11:13 909 17350714 21147558 5.37 4.4

methyl(methylethyl)-benzene 11:17 826 15391020 21147558 5.37 3.9

Limonene 11:26 919 41226592 21147558 5.37 10.5

methyl(methylethyl)-

cyclohexene12:10 3680440

Pinene* 12:20 15177180

Pinene* 12:27 21213656

Pinene* 12:50 4620421

Pinene* 13:15 10777788

Sample ID: A-4






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

(ppm)

Acetone 1:40 919 3378059

Dimethyl Sulfide 1:49 814 2143283

2-Butanone 2:09 916 4093026 20092514 5.37 1.1



Pinene* 9:54 1410698

Pinene 10:03 934 54449476 20092514 5.37 14.6

Pinene* 10:38 32660390

Pinene* 10:44 57988016

3-Carene 11:12 917 17581546 20092514 5.37 4.7

methyl(methylethyl)-benzene 11:17 839 16719400 20092514 5.37 4.5

Limonene 11:25 916 45038396 20092514 5.37 12.0

methyl(methylethyl)-

cyclohexene12:10 825 4097453 20092514 5.37 1.1

Pinene* 12:19 14526550

Pinene* 12:27 18569342

Pinene* 13:14 6156172

Sample ID: A-5






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

(ppm)

Acetone 1:40 931 2950662


2-Butanone 2:08 913 4288270 20525890 5.37 1.1

2-Pentanone 2:40 795 1875393

Hexane 2:47 733 1848477

Pinene 10:04 942 80676784 20525890 5.37 21.1

Pinene* 10:38 43044548

Pinene* 10:44 87686304

3-Carene 11:13 930 53885500 20525890 5.37 14.1

Limonene 11:25 911 50120624 20525890 5.37 13.1

Pinene* 12:19 15839246

Pinene* 12:26 21655408

Pinene* 12:48 6414475

Sample ID: A-6






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

(ppm)

Acetone 1:40 853 2881815


2-Butanone 2:09 931 5443676 24076846 5.37 1.2

2-Pentanone 2:40 768 2400917

MethylButanal 2:48 752 2162916


Hexanoic acid, methyl ester 9:34 849 5527830 24076846 5.37 1.2

Pinene* 9:55 2871757

Pinene 10:05 939 138814608 24076846 5.37 31.0

Pinene* 10:40 58109112

Pinene* 10:46 148963120

3-Carene 11:14 929 50120624 24076846 5.37 11.2

Limonene 11:27 916 87048040 24076846 5.37 19.4

Pinene* 12:12 7603220

Pinene* 12:22 24553652

Pinene* 12:29 29765092

methyl-methylethyl-

cyclohexenol13:17 15421734

Sample ID: A-7






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

(ppm)

Acetone 1:41 932 2500463

2-Butanone 2:09 915 4787324 19534536 5.37 1.3

2-Pentanone 2:41 764 1986763



m,p-Xylene 8:26 839 8618205 19534536 5.37 2.4


Pinene 10:04 935 141927936 19534536 5.37 39.0

Pinene* 10:38 86849360

Pinene* 10:44 155937968

3-Carene 11:12 927 97384568 19534536 5.37 26.8

Limonene 11:25 908 78173848 19534536 5.37 21.5

Pinene* 12:18 25133608

Pinene* 12:26 31663814

methyl-methylethyl-


Sample ID: A-8






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

Acetone 1:42 915 22529546

2-Butanone 2:11 855 15070542

2-Pentanone 2:41 764 5295845

Benzene 2:52 902 4348279

Pentanol 4:03 10329461

Toluene 4:57 941 12036943

o-Xylene 9:02 789 1854496


Pinene 10:06 47218848

3-Carene 11:14 3473524

methyl-methylethyl-benzene 11:19 12048343

Limonene 11:27 831 8942538

Pinene* 12:29 23220850

Pinene* 12:51 15619587

methyl-methylethyl-


Sample ID: A-9





instrument specific research. Compounds could not be quantified

due to tedlar bag contaminant interference.

Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

Nitromethane 1:57 882 14461667

2-Butanone 2:11 891 3060594

Toluene 4:57 907 3590854

Pinene 10:06 886 10114802

Limonene 11:27 786 1160969

Sample ID: A-10



Notes: Compounds could not be quantified due to tedlar bag

contaminant interference.

Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

Nitromethane 1:57 857 12115907

Toluene 4:57 925 4751440

Pinene 10:06 883 5279913

Sample ID: A-11



Notes: Compounds could not be quantified due to tedlar bag

contaminant interference.

Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

Pinene 10:03 811 7107330 23999720 20 5.9

Limonene 11:24 751 749081

Sample ID: A-12



Notes: Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

Styrene 8:52 806 1237201 23189540 20 1.1

Pinene* 9:52 835 906168

Pinene 10:02 957 850254720 23189540 20 733.3

Pinene* 10:42 34259152

methyl-methylethyl-benzene 11:15 13337257

Limonene 11:23 927 169765104 23189540 20 146.4

Pinene* 12:27 22349860

Pinene* 12:46 10422893

Pinene* 13:19 72326656

Sample ID: A-13






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration


Sample ID: B-1



(ppb level detection range)


Sample Location:

PSCAA GC-MS Evaluation Data - Site B Final.xlsx Prepared by KD Analytical B-1


TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration


Sample ID: B-2



Notes: No compounds detected within instrument parameters

(ppp level detection range)

Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

Acetone 1:41 786 34814036 27982750 20 24.9

2-Butanone 2:11 836 2684437 27982750 20 1.9

Pinene 10:05 907 16285153 27982750 20 11.6

Pinene* 10:45 11965138

3-Carene 11:14 904 3918880 27982750 20 2.8

methyl-(methylethyl)-benzene 11:18 5787476

Limonene 11:26 927 39310828 27982750 20 28.1

Pinene* 12:21 3593580

Pinene* 12:28 5801852

Sample ID: B-3






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

2-Butanone 2:11 784 602642

Pinene 10:05 925 10366645 26785586 20 7.7

Pinene* 10:39 5060579

Pinene* 10:45 11468784

3-Carene 11:14 904 2521989 26785586 20 1.9


Limonene 11:27 919 24938850 26785586 20 18.6

Pinene* 12:21 4157048

Sample ID: B-4






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

Dimethyl sulfide 1:50 905 2485868 26024706 20 1.9

2-Butanone 2:10 887 2919051 26024706 20 2.2

Pinene 10:05 945 35663640 26024706 20 27.4

Pinene* 10:39 13085549

Pinene* 10:45 22770826

3-Carene 11:13 930 109152248 26024706 20 83.9


Limonene 11:26 920 100832032 26024706 20 77.5

Cyclohexadiene^ 11:47 7844523

Pinene* 12:21 59826420

Sample ID: B-5





instrument specific research. ^Cyclohexadiene compound type

cannot be specified

Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

Ethanol 1:38 969 47876068 10488028 20 91.3


2-Butanone 2:11 930 3272013 10488028 20 6.2

Methyl-Cyclohexane 4:07 864 5666904 10488028 20 10.8

Toluene 4:57 858 1549399 10488028 20 3.0

Octane 6:18 722 6084045 10488028 20 11.6

Pinene 10:05 843 88746040 10488028 20 169.2

Pinene* 10:39 233927312

Pinene* 10:44 385909088

3-Carene 11:13 889 37084132 10488028 20 70.7

Limonene 11:26 909 120918192 10488028 20 230.6

Pinene* 12:20 60420120

Sample ID: B-6






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

(ppm)

Dimethyl sulfide 1:50 843 23017092 24451986 5.37 5.1

2-Butanone 2:09 883 6843453 24451986 5.37 1.5

ethyl furan 3:24 2404417

Heptane 3:35 849 2571007

Toluene 4:54 947 13265856 24451986 5.37 2.9

Octane 6:19 896 8247818 24451986 5.37 1.8

Nonane 9:24 901 5900481 24451986 5.37 1.3

Pinene* 9:54 20976634

Pinene 10:05 952 568219200 24451986 5.37 124.8

Pinene* 10:39 48863440

Pinene* 10:46 276137440

3-Carene 11:14 938 53547536 24451986 5.37 11.8


Limonene 11:26 921 98734800 24451986 5.37 21.7

Pinene* 12:21 13031192

Pinene* 12:40 46423184

Pinene* 13:00 53669828

Pinene* 13:16 65410996

Pinene* 13:39 51427788

Sample ID: B-7






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

Butene 1:31 1581462

2-Butanone 2:10 929 9076996 5870737 20 30.9

2-Butanol 2:14 887 8316076 5870737 20 28.3

Heptane 3:35 864 6910836 5870737 20 23.5

Pentanoic Acid 5:41 781 9085495 5870737 20 31.0

Butanoic acid, ethyl ester 5:47 777 15134078 5870737 20 51.6

Octane 6:19 855 5014832 5870737 20 17.1

Pinene* 9:55 7954999

Pinene 10:05 952 247434224 5870737 20 842.9

Pinene* 10:45 546271744

3-Carene 11:13 890 126590752 5870737 20 431.3

Limonene 11:26 921 240117744 5870737 20 818.0

Pinene* 12:20 31067036

Sample ID: B-8






Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration

(ppb)

Butene 1:31 5518926


2-Butanone 2:10 881 34007288 11065099 20 61.5

2-Butanol 2:14 865 62722044 11065099 20 113.4

Methyl furan 2:22 62381828

Ethyl furan 3:27 66195448

Heptane 3:36 887 38570308 11065099 20 69.7

Toluene 4:57 934 9342909 11065099 20 16.9

Butanoic Acid 5:39 722 8730961 11065099 20 15.8

Butanoic acid, ethyl ester 5:49 767 8521696 11065099 20 15.4

Octane 6:19 919 55876700 11065099 20 101.0

Nonane 9:25 886 25328642 11065099 20 45.8

Pinene* 9:56 253728320

Pinene 10:07 960 3546254336 11065099 20 6409.8

Pinene* 10:39 553499392

Pinene* 10:46 1255838464

3-Carene 11:13 911 876138432 11065099 20 1583.6

Limonene 11:13 930 126590752 11065099 20 228.8

Cyclohexadiene 11:48 148037728

methyl

(methylethyl)cyclohexene12:11 49607444

Pinene* 12:20 156665152

Sample ID: B-9





instrument specific research. Pinene concentration is greater than

reported. Full area could not be attained due to a concentration

above method detection limits. ^Cyclohexadiene compound type

cannot be specified

Sample Time:




instrument specific research. Pinene concentration is greater than

reported. Full area could not be attained due to a concentration

above method detection limits. ^Cyclohexadiene compound type

cannot be specified



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

(ppm)

Toluene 4:53 925 3081605

Limonene 11:27 913 10186510 25671410 5.37 2.1

Sample ID: B-10



Notes: Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

(ppm)

Limonene 11:27 895 5717908 27254350 5.37 1.1

Sample ID: B-11



Notes: Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration


Sample ID: C-1





PSCAA GC-MS Evaluation Data - Site C Final.xlsx Prepared by KD Analytical C-1


TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppm

Approximate

Compound

Concentration

(ppm)

Hexane 2:19 819 5250430 20501518 5.37 1.4

Methylcyclopentane 2:37 842 2745006

Heptane 3:35 829 2258357

Methylcyclohexane 4:06 816 3814871

Toluene 4:56 914 7702980 20501518 5.37 2.0

Dimethylcyclohexane 5:38 810 1945522

Ethylhexane 6:20 754 2275385

1-chloro-4-(trifluoromethyl)-

Benzene7:52 915 9782174 20501518 5.37 2.6

Ethylbenzene 8:13 874 6994145 20501518 5.37 1.8

m, p-xylene 8:28 952 18623196 20501518 5.37 4.9

o-xylene 9:02 922 4232908 20501518 5.37 1.1

Nonane 925 809 878170

Methylethylbenzene 10:24 841 642251

Trimethylbenzene 10:53 763 716914

Decane 11:04 784 689068

Limonene 11:28 889 7403371 20501518 5.37 1.9

Sample ID: C-2


Notes: Sample Time:




TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration


Sample ID: C-3





Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration


Sample ID: C-4





Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration


Sample ID: C-5





Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration


Sample ID: C-6





Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration


Sample ID: C-7





Sample Time:



TimeNIST SI

Area Count of

Compound

Area Count of

BPFB (IS)

Concentration

of BPFB (IS)

ppb

Approximate

Compound

Concentration


Sample ID: C-8





Sample Time:


APPENDIX B

evaluation of a portable field operated gc/ms instrument

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